Renewably Derived Polyesters and Methods of Making and Using the Same

ABSTRACT

Polyester compositions are disclosed herein, as well as methods of making and using such polyesters. In some embodiments, the polyesters are formed from monomers derived from natural oils.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/487,254, filed Apr. 13, 2017, which claims the benefit ofU.S. Provisional Application No. 62/325,444, filed Apr. 20, 2016, whichare hereby incorporated by reference as though set forth herein in theirentireties.

TECHNICAL FIELD

Polyester compositions are disclosed herein, as well as methods ofmaking and using such polyesters. In some embodiments, the polyestersare formed from monomers derived from natural oils.

BACKGROUND

Polyesters are polymers that contain a plurality of ester linkages.Polyesters are one of the most widely used polymers for commercialapplications. In fact, after polyolefins, polyesters are the most widelyused polymers for commercial applications. The most commonly usedpolyester is polyethylene terephthalate (PET). Other commonly usedpolyesters include polybutylene terephthalate (PBT), polybutylenesuccinate (PBS), polyethylene adipate (PEA), polycaprolactone (PCL), andpolylactic acid (PLA).

In many cases, polyesters are formed from monomers that are derived fromrefining petroleum products. Such processes generally involve crackingand refining crude petroleum to obtain olefin fragments having a smallnumber of carbon atoms (e.g., two or three carbons). To formlonger-chain compounds, the fragments must be reacted to with other suchfragments and/or other compounds to form compounds having longer carbonchains. This process is energy-intensive and time-intensive. Further,such processes contribute to the further depletion of non-renewablesources of carbonaceous material.

There are some exceptions, such as polylactic acid (PLA). In fact, PLAhas the second highest consumption of any renewably derived polymer inuse today. But its use is generally limited to situations whereresistance to degradation is not an issue. For example, PLA is widelyused in making biodegradable materials, such as medical implants,disposable cups, and the like. But there are a very limited number ofpolymers made from renewably derived monomers that exhibit chemical andphysical characteristics closer to those of more commonly usedpolyesters.

Refining processes for natural oils (e.g., employing metathesis) canlead to compounds having carbon-chain lengths closer to those generallydesired for chemical intermediates of specialty chemicals (e.g., about 9to 15 carbon atoms). Thus, the refining of natural oils may, in manyinstances, provide a more chemically efficient and straightforward wayto make certain monomers for use in making polymeric species, such aspolyesters. Further, because such compounds contain a certain degree ofinherent functionality that is otherwise absent from petroleum-sourcedmaterials, it may often be more desirable, if not cheaper, to usenatural oils or their derivatives as a starting point for making certaincompounds. Additionally, natural oils and their derivatives aregenerally sourced from renewable feedstocks. Thus, by using suchstarting materials, one can enjoy the concomitant advantage ofdeveloping useful chemical products without consuming limited suppliesof petroleum.

Thus, there is a continuing need to discover novel polyesters that areformed using monomers derived from renewable sources, such as naturaloils.

SUMMARY

In a first aspect, the disclosure provides polyester polymers, whichinclude constitutional units formed from a reaction mixture comprisingone of more monomers of Formula (Ia):

and one or more monomers for Formula (Ib):

wherein R¹ is —OH or —OR³; R² is —O—(C₁₋₆ alkyl); R³ is C₁₋₆ alkyl orC₁₋₆ oxyalkyl; X¹ is C₄₋₁₀ alkylene; R¹¹ is —OH or —OR¹³; R¹² is—O—(C₁₋₆ alkyl); R¹³ is C₁₋₆ alkyl or C₁₋₆ oxyalkyl; and X¹¹ is C₄₋₁₀alkylene.

In a second aspect, the disclosure provides a coating composition, thecomposition including polyester polymers of the first aspect. In someembodiments, the coating composition includes one or more additionalpolymers. In some such embodiments, the one or more additional polymershave a higher glass transition temperature than the polyester polymersof the first aspect.

In a third aspect, the disclosure provides a personal care composition,the composition including polyester polymers of the first aspect. Insome embodiments, the personal care composition includes one or moreadditional ingredients. Non-limiting examples of personal carecompositions include shampoos, hair conditioners, skin moisturizers,hair-styling products, and the like.

In a fourth aspect, the disclosure provides an ink composition, thecomposition including polyester polymers of the first aspect. In someembodiments, the ink compositions include one or more additionalingredients.

In a fifth aspect, the disclosure provides a rheology modifiercomposition, the composition including polyester polymers of the firstaspect. In some embodiments, the rheology modifier compositions includeone or more additional ingredients.

In a sixth aspect, the disclosure provides a polyurethane blockcopolymer, wherein at least one of the blocks of the block copolymerincludes a polyester polymer of the first aspect. In some embodiments,one or more of the other blocks in the block copolymer include apolycarbamate polymer.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

The FIGURE shows a monomer useful for forming constitutional unitsmaking up the polyesters disclosed herein, wherein R¹ is a hydroxylgroup or an ether or polyether functional group, and X¹ is an alkylenegroup.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “polymer” refers to a substance having a chemicalstructure that includes the multiple repetition of constitutional unitsformed from substances of comparatively low relative molecular massrelative to the molecular mass of the polymer. The term “polymer”includes soluble and/or fusible molecules having chains of repeat units,and also includes insoluble and infusible networks. As used herein, theterm “polymer” can include oligomeric materials, which have only a few(e.g., 5-100) constitutional units

As used herein, “monomer” refers to a substance that can undergo apolymerization reaction to contribute constitutional units to thechemical structure of a polymer.

As used herein, “copolymer” refers to a polymer having constitutionalunits formed from more than one species of monomer.

As used herein, “block copolymer” refers to a copolymer having two ormore different blocks of polymerized monomers, i.e., different polymersequences.

As used herein, “polyurethane” refers to a polymer comprising two ormore urethane (or carbamate) linkages. Other types of linkages can beincluded, however. For example, in some instances, the polyurethane orpolycarbamate can contain urea linkages, formed, for example, when twoisocyanate groups can react. In some other instances, a urea or urethanegroup can further react to form further groups, including, but notlimited to, an allophanate group, a biuret group, or a cyclicisocyanurate group. In some embodiments, at least 70%, or at least 80%,or at least 90%, or at least 95% of the linkages in the polyurethane orpolycarbamate are urethane linkages. Further, in the context of a blockcopolymer, the term “polyurethane block copolymer” refers to a blockcopolymer, where one or more of the blocks are a polyurethane or apolycarbamate. Other blocks in the “polyurethane block copolymer” maycontain few, if any, urethane linkages. For example, in somepolyurethane block copolymers, at least one of the blocks is a polyetheror a polyester and one or more other blocks are polyurethanes orpolycarbamates.

As used herein, “polyester” refers to a polymer comprising two or moreester linkages. Other types of linkages can be included, however. Insome embodiments, at least 80%, or at least 90%, or at least 95% of thelinkages between monomers in the polyester are ester linkages. The termcan refer to an entire polymer molecule, or can also refer to aparticular polymer sequence, such as a block within a block copolymer.

As used herein, “copolymer” refers to a polymer having constitutionalunits formed from more than one species of monomer.

As used herein, “block copolymer” refers to a copolymer having two ormore different blocks of polymerized monomers, i.e., different polymersequences.

As used herein, “polyurethane” or “polycarbamate” refers to a polymercomprising two or more urethane (or carbamate) linkages. Other types oflinkages can be included, however. For example, in some instances, thepolyurethane or polycarbamate can contain urea linkages, formed, forexample, when two isocyanate groups can react. In some other instances,a urea or urethane group can further react to form further groups,including, but not limited to, an allophanate group, a biuret group, ora cyclic isocyanurate group. In some embodiments, at least 70%, or atleast 80%, or at least 90%, or at least 95% of the monomer linkages inthe polyurethane or polycarbamate are urethane linkages. Further, in thecontext of a block copolymer, the term “polyurethane block copolymer”refers to a block copolymer, where one or more of the blocks are apolyurethane or a polycarbamate. Other blocks in the “polyurethane blockcopolymer” may contain few, if any, urethane linkages. For example, insome polyurethane block copolymers, at least one of the blocks is apolyether or a polyester and one or more other blocks are polyurethanesor polycarbamates.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms; and “C_(x-y)”, which refers to a group or compoundcontaining from x to y, inclusive, carbon atoms. For example, “C₁₋₆alkyl” represents an alkyl chain having from 1 to 6 carbon atoms and,for example, includes, but is not limited to, methyl, ethyl, n-propyl,isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl,n-pentyl, neopentyl, and n-hexyl. As a further example, a “C₄₋₁₀ alkene”refers to an alkene molecule having from 4 to 10 carbon atoms, and, forexample, includes, but is not limited to, 1-butene, 2-butene, isobutene,1-pentene, 1-hexene, 3-hexene, 1-heptene, 3-heptene, 1-octene, 4-octene,1-nonene, 4-nonene, and 1-decene.

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins includealpha-olefins, wherein the unsaturated carbon-carbon bond is present atone end of the compound. Low-molecular-weight olefins may also includedienes or trienes. Low-molecular-weight olefins may also includeinternal olefins or “low-molecular-weight internal olefins.” In certainembodiments, the low-molecular-weight internal olefin is in the C₄₋₁₄range. Examples of low-molecular-weight olefins in the C₂₋₆ rangeinclude, but are not limited to: ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1,4-pentadiene,1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, andcyclohexene. Non-limiting examples of low-molecular-weight olefins inthe C₇₋₉ range include 1,4-heptadiene, 1-heptene, 3,6-nonadiene,3-nonene, 1,4,7-octatriene. Other possible low-molecular-weight olefinsinclude styrene and vinyl cyclohexane. In certain embodiments, it ispreferable to use a mixture of olefins, the mixture comprising linearand branched low-molecular-weight olefins in the C₄₋₁₀ range. Olefins inthe C₄₋₁₀ range can also be referred to as “short-chain olefins,” whichcan be either branched or unbranched. In one embodiments, it may bepreferable to use a mixture of linear and branched C₄ olefins (i.e.,combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C₁₁₋₁₄ may be used.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin ester”or “olefinic ester compounds.” Further, a “terminal olefinic estercompound” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, “alcohol” or “alcohols” refer to compounds having thegeneral formula: R—OH, wherein R denotes any organic moiety (such asalkyl, aryl, or silyl groups), including those bearingheteroatom-containing substituent groups. In certain embodiments, Rdenotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments,the term “alcohol” or “alcohols” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. The term “hydroxyl” refers to a —OH moiety. Insome cases, an alcohol can have two or more hydroxyl groups. As usedherein, “diol” refers to alcohols having two or more hydroxyl groups.

As used herein, “carboxylic acid” or “carboxylic acids” refer tocompounds having the general formula: R—C(O)—OH, wherein R denotes anyorganic moiety (such as alkyl, aryl, or silyl groups), including thosebearing heteroatom-containing substituent groups. In certainembodiments, R denotes alkyl, alkenyl, aryl, or alcohol groups. Incertain embodiments, the term “carboxylic acid” or “carboxylic acids”may refer to a group of compounds with the general formula describedabove, wherein the compounds have different carbon lengths. The term“carboxyl” refers to a —C(O)OH moiety. In some cases, a carboxylic acidcan have two or more hydroxyl groups. As used herein, “dicarboxylicacid” and “diacid” refer to carboxylic acids having two or more carboxylgroups.

As used herein, “hydroxy acid” or “hydroxy acids” refer to compoundshaving the general formula: HO—R—C(O)—OH, wherein R denotes any organicmoiety (such as alkyl, aryl, or silyl groups), including those bearingheteroatom-containing substituent groups. In certain embodiments, Rdenotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments,the term “hydroxy acid” or “hydroxy acids” may refer to a group ofcompounds with the general formula described above, wherein thecompounds have different carbon lengths.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y) alkyl,” which refersto an alkyl group, as herein defined, containing from x to y, inclusive,carbon atoms. Thus, “C₁₋₆ alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group. Also, in someinstances, one or more of the carbon atoms in the alkyl or alkylenegroup can be replaced by a heteroatom (e.g., selected from nitrogen,oxygen, or sulfur, including N-oxides, sulfur oxides, and sulfurdioxides, where feasible), and is referred to as a “heteroalkyl” or“heteroalkylene” group, respectively. Non-limiting examples include“oxyalkyl” or “oxyalkylene” groups, which include groups of thefollowing formulas: -[-(alkylene)-O-]_(x)-alkyl,-[-(alkylene)-O-]_(x)-alkylene-, respectively, where x is 1 or more,such as 1, 2, 3, 4, 5, 6, 7, or 8.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week, or a compound which maintains its integrity long enoughto be useful for therapeutic or prophylactic administration to apatient. As used herein, the phrases “substituted with one or more . . .” or “substituted one or more times . . . ” refer to a number ofsubstituents that equals from one to the maximum number of substituentspossible based on the number of available bonding sites, provided thatthe above conditions of stability and chemical feasibility are met.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Polyester Polymers

In a first aspect, the disclosure provides polyester polymers, whichinclude constitutional units formed from one of more monomers of Formula(Ia):

and constitutional units formed from one or more monomers for Formula(Ib):

wherein R¹ is —OH or —OR³; R² is —O—(C₁₋₆ alkyl); R³ is C₁₋₆ alkyl orC₁₋₆ oxyalkyl; X¹ is C₄₋₁₀ alkylene; R¹¹ is —OH or —OR¹³; R¹² is—O—(C₁₋₆ alkyl); R¹³ is C₁₋₆ alkyl or C₁₋₆ oxyalkyl; and X¹¹ is C₄₋₁₀alkylene.

In some embodiments of any of the aforementioned embodiments, R¹ is —OH.In some embodiments of any of the aforementioned embodiments, R¹ is—OR³. In some such embodiments, R³ is methyl, ethyl, or isopropyl. Insome further such embodiments, R³ is methyl.

In some embodiments of any of the aforementioned embodiments, R² ismethyloxy, ethyloxy, or n-propyloxy. In some such embodiments, R² ismethyloxy.

In some embodiments of any of the aforementioned embodiments, X¹ is—(CH₂)₇—.

In some embodiments of any of the aforementioned embodiments, R¹¹ is—OH. In some embodiments of any of the aforementioned embodiments, R¹¹is —OR¹³. In some such embodiments, R¹³ is methyl, ethyl, or isopropyl.In some further such embodiments, R¹³ is methyl.

In some embodiments of any of the aforementioned embodiments, R¹² ismethyloxy, ethyloxy, or n-propyloxy. In some such embodiments, R¹² ismethyloxy.

In some embodiments of any of the aforementioned embodiments, X¹¹ is—(CH₂)₇—.

The polyester polymers disclosed herein can contain constitutional unitsformed from compounds of Formula (Ia) and constitutional units formedfrom compounds of Formula (Ib) in any suitable ratio. In someembodiments, the molar ratio of constitutional units formed frommonomers of Formula (Ia) to constitutional units formed from monomers ofFormula (Ib) is from 1:10 to 10:1.

The polyester polymers disclosed herein can have any suitable type. Insome embodiments of any of the aforementioned embodiments, the polyesterpolymer is an AB/AB′-type polymer.

The polyester polymers disclosed herein can have any suitable molecularweight. In some embodiments, the polyester polymers have anumber-average molecular weight ranging from 1,000 Da to 50,000 Da, orfrom 1,000 Da to 40,000 Da, or from 1,000 Da to 30,000 Da, or from 2,000Da to 20,000 Da.

The polyester polymers disclosed herein can have any suitable physicalproperties. In some embodiments, the polyester polymer is athermoplastic polymer. In some embodiments, the polyester polymer isbiodegradable. In some embodiments, the polyester polymer issemi-crystalline.

The polyester polymers can include any additional constitutional unitsformed from other monomers, such as diols, dicarboxylic acids (diacids)or esters thereof, and/or hydroxyl acids or esters thereof. In someembodiments of any of the aforementioned embodiments, the reactionmixture further comprises one or more diols. In some embodiments, theone or more diols are selected from the group consisting of ethyleneglycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol,2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol,2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, and neopentylglycol. In some embodiments of any of the aforementioned embodiments,the reaction mixture further comprises constitutional units formed fromone or more diacids, or esters thereof (such as C₁₋₆ alkyl esters, e.g.,dimethyl esters). In some embodiments, the one or more diacids, oresters thereof, are selected from the group consisting of oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid,1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid,1,18-octadecanedioic acid, 1,20-eicosanedioic acid, 1,22-docosanedioicacid, 1,18-octadec-9-enedioic acid, and esters of any of the foregoing.In some embodiments of any of the foregoing embodiments, the reactionmixture further comprises one or more hydroxy acids, or esters thereof.In some embodiments, the one or more hydroxy acids, or esters thereof,are selected from the group consisting of α-hydroxy acids (such asglycolic acid, lactic acid, malic acid, citric acid, tartaric acid, andthe like), β-hydroxy acids (such as 3-hydroxypropionic acid,3-hydroxybutanoic acid, 3-hydroxy-3-methylbutanoic acid, and the like),ω-hydroxy acids (such as 16-hydroxypalmitic acid, 18-hydroxystearicacid, and the like), and esters of any of the foregoing.

The polyester polymers disclosed herein can include certain additivesthat may play a role in tuning the properties. For example, in someembodiments, the reaction mixture further comprises one or morebranching agents. In some embodiments, the reaction mixture furthercomprises one or more cross-linking agents.

Compositions Including the Polyester Polymers

The aforementioned polyester polymers can be included in any suitablecompositions, such as coating compositions, personal care compositions,and adhesive compositions.

For example, in certain aspects and embodiments, the disclosure providescoating compositions that include polyester polymers of any of theforegoing embodiments. Such coating compositions can include anyadditional additives and polymers, such as are commonly included incoating compositions, such as pigments, coalescents, additional resins,and the like. The coating compositions can be suitable for coating anysuitable surface, including, but not limited to, plastic, metal, wood,stone, concrete, glass, and the like.

In certain other aspects and embodiments, the disclosure providespersonal care compositions that include polyester polymers of any of theforegoing embodiments. Such personal care compositions can include anyadditional additives and polymers, such as are commonly included inpersonal care compositions, such as hydrocarbons, waxes, glycerideesters, surfactants, and the like.

In certain other aspects and embodiments, the disclosure provides inkcompositions that include polyester polymers of any of the foregoingembodiments. Such ink compositions can include any additional additivesand polymers, such as are commonly included in ink compositions, such assolvents, pigments, dyes, and the like.

In certain other aspects and embodiments, the disclosure providesrheology modifier compositions that include polyester polymers of any ofthe foregoing embodiments. Such rheology modifier compositions caninclude any additional additives and polymers, such as are commonlyincluded in rheology modifier compositions.

In certain other aspects and embodiments, the disclosure providesadhesive compositions that include polyester polymers of any of theforegoing embodiments. Such adhesive compositions can include anyadditional additives and polymers, such as are commonly included inadhesive compositions, such as tackifiers, waxes, rosin oils, and thelike.

Block Copolymers

In certain aspects and embodiments, the disclosure provides certainblock copolymers in which the polyester polymers of any of the foregoingembodiments can serve as one of the blocks in the block copolymer. Anysuitable block copolymers can be formed, including, but not limited to,diblock copolymers, triblock copolymers, and the like. In addition tothe polyester block the other block(s) can include any suitablepolymeric chain. For example, in some embodiments, the block copolymercomprises a second block that includes polycaprolactone. In some otherembodiments, the block copolymer comprises a second block that includesa polycarbamate. In some such embodiments, the block copolymer is athermoplastic polyurethane (TPU). In some other embodiments, the blockcopolymer comprises a second block that includes another polyester. Insome other embodiments, the block copolymer comprises a second blockthat includes a polyamide. In some other embodiments, the blockcopolymer comprises a second block that includes a polyamide ester. Insome embodiments of any of the aforementioned embodiments, the blockcopolymer is biodegradable. Any of the foregoing block copolymers canalso be used in any of the types of compositions described in theimmediately preceding section.

Derivation from Renewable Sources

The compounds employed in any of the aspects or embodiments disclosedherein can, in certain embodiments, be derived from renewable sources,such as from various natural oils or their derivatives. Any suitablemethods can be used to make these compounds from such renewable sources.Suitable methods include, but are not limited to, fermentation,conversion by bioorganisms, and conversion by metathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275595, and 2014/0275681, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above).

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described below with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above).

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The reactor design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

EXAMPLES Materials

Methyl 9-decenoate (9-DAME) was provided from Elevance RenewableSciences, Inc., and used as received. Dibutyltin oxide (SnOBu₂; 98%),meta-chloroperoxybenzoic acid (m-CPBA, ≤77%), magnesium sulfate (MgSO₄,99%) sodium sulfite (NaSO₃, ≥98%), sodium bicarbonate (NaHCO₃, ≥99.7),and sodium chloride (NaCl, ≥99%) were obtained from Sigma Aldrich andused as received. Sodium methoxide (NaOMe, 0.5 M solution in methanol(MeOH)) were obtained from Acros Organics and used as received.Dichloromethane (DCM) and diethyl ether (anhydrous, stabilized with BHT)were obtained from Fisher Scientific and used as received. All waterused was purified using a reverse osmosis process.

Example 1—Monomer Synthesis

In order as listed, m-CPBA (58.45 g), DCM (˜425 mL), and 9-DAME (45 mL)were added to a round-bottomed flask equipped with a magnetic stir bar.The round-bottomed flask was placed in a water bath and allowed to stirfor multiple days. The white solid precipitate was filtered out and thereaction allowed to sit in a −20° C. freezer for further precipitation.The white precipitate was again removed using vacuum filtration and thefreezing/filtration process repeated until no further precipitateformed. The reaction was then washed with a sodium bisulfite solutionand extracted into DCM. The organic layer was then washed three timeswith a saturated sodium bicarbonate solution and the organic layerscombined and solvent removed using rotary evaporation. The product wasthen placed in a −20° C. freezer overnight and filtered through a 5 μmmembrane filter. Washing and freezer precipitation were repeated until¹H NMR revealed minimal m-CPBA/meta-chlorobenzoic acid (m-CBA) remained.Epoxidized 9-DAME was then dried in a vacuum oven at −50° C. overnight.Epoxidized 9-DAME (5.02 g, 1.0 mol equivalents) was added to a dryround-bottomed flask equipped with a magnetic stir bar. 0.5 M NaOMesolution (60 mL, 1.2 mol equivalents) was added to the reaction usingdry technique. The reaction was lowered into a room temperature oil bathand stirred with a slow N₂ purge overnight. The N₂ purge was thenstopped and the reaction placed into a 75° C. oil bath with stirring for5 d. MeOH was removed using rotary evaporation and the following workupprocedure ensued, adapted from that set forth in Creary et al, J. Org.Chem., vol. 42, p. 4226 (1977). The reaction was dissolved in aMeOH/diethyl ether mixture and washed with brine. The aqueous layer wasreextracted with both diethyl ether and brine and the combined organiclayers were washed with brine three times, dried over magnesium sulfate,filtered, and the solvent removed using rotary evaporation. The productwas then dried in a vacuum oven at ˜50-60° C. overnight.

Example 2—Polymerization

An isomeric mixture of 0.26 g AB ether-containing monomer (methyl9-hydroxy-10-methoxydecanoate and methyl 10-hydroxy-9-methoxydecanoate)was added to a dry 50 mL round-bottomed flask. 600 ppm SnOBu₂ (˜0.0003g) catalyst was added to the reaction and the round-bottomed flask wasfit with a mechanical stirrer, t-neck, and distillation apparatus. A N₂and vacuum purge, repeated three times, ensured removal of oxygen priorto starting the reaction. The reaction was lowered into a Si oil bathwith a target temperature of 80° C. and allowed to stir whilemaintaining a constant N₂ purge. After 2 h, the oil bath temperature wasincreased to 130° C. for another 2 h, followed by an increase to 200° C.for 0.5 h. Vacuum (at least 0.15 mmHg) was applied while the reactionwas at 200° C. and stirring and allowed to proceed for 2 h. The reactionwas then removed from the oil bath and cooled under a N₂ atmosphere. Thereaction setup was disassembled and the product was removed from theround-bottomed flask. Characterization proceeded without anypurification. Note: Gelation occurred during the vacuum step suggestingsome f=3 monomer and/or side reactions are occurring at the elevatedtemperatures in the presence of the tin catalyst. Varying catalyst typeand amount will allow for a further investigation.

1-31. (canceled)
 32. A block copolymer, which comprises a first blockand a second block, wherein the first block comprises a polyesterpolymer comprising constitutional units formed from a reaction mixturecomprising one of more monomers of Formula (Ia):

and one or more monomers for Formula (Ib):

wherein: R¹ is —OH or —OR³; R² is —O—(C₁₋₆ alkyl); R³ is C₁₋₆ alkyl orC₁₋₆ oxyalkyl; X¹ is C₄₋₁₀ alkylene; R¹¹ is —OH or —OR′³; R¹² is—O—(C₁₋₆ alkyl); R¹³ is C₁₋₆ alkyl or C₁₋₆ oxyalkyl; and X¹¹ is C₄₋₁₀alkylene.
 33. The block copolymer of claim 32, where the second blockcomprises a poly(alkylene oxide).
 34. The block copolymer of claim 33,wherein the poly(alkylene oxide) is selected from the group consistingof poly(ethylene oxide), poly(1,2-propylene oxide), andpoly(1,3-propylene oxide).
 35. The block copolymer of claim 32, whereinthe second block comprises polycaprolactone.
 36. The block copolymer ofclaim 32, wherein the second block comprises a polycarbamate.
 37. Theblock copolymer of claim 32, wherein the second block comprises apolyester.
 38. The block copolymer of claim 32, wherein the second blockcomprises a polyamide.
 39. The block copolymer of claim 32, wherein thesecond block comprises a polyamide ester.
 40. The block copolymer ofclaim 32, wherein R¹ is —OH.
 41. The block copolymer of claim 32,wherein R¹ is —OR³.
 42. The block copolymer of claim 41, wherein R³ ismethyl.
 43. The block copolymer of claim 32, wherein R² is methyloxy,ethyloxy, or n-propyloxy.
 44. The block copolymer of claim 32, whereinX¹ is —(CH₂)₇—.
 45. The block copolymer of claim 32, wherein R¹¹ is —OH.46. The block copolymer of claim 32, wherein R¹¹ is —OR¹³.
 47. The blockcopolymer of claim 46, wherein R¹³ is methyl, ethyl, or isopropyl. 48.The block copolymer of claim 32, wherein R¹³ is methyl.
 49. The blockcopolymer of claim 43, wherein R¹² is methyloxy, ethyloxy, orn-propyloxy.
 50. The block copolymer of claim 43, wherein X¹¹ is—(CH₂)₇—.
 51. The block copolymer of claim 32, wherein the reactionmixture comprises one or more diols.
 52. The block copolymer of claim32, wherein the reaction mixture further comprises one or more diacids,or esters thereof.
 53. The block copolymer of claim 32, wherein thereaction mixture further comprises one or more hydroxy acids, or estersthereof.